Antimicrobial detergent compositions



3,244,636 ANTIMICROBIAL DETERGENT COMPOSITIONQ Herbert H. Reller and Herbert Quinn, Green Township, Hamilton County, Ohio, assignors to The Procter 8: gamble Company, Cincinnati, Ohio, a corporation of No Drawing. Filed July 29, 1963, Ser. No. 298,491 13 Claims. (Cl. 252-107) This invention relates to cleansing and detergent compositions which in addition to effectively removing soil also possess antimicrobial activitiy. More especally, this invention relates to antimicrobial detergent compositions which contain as the primary antimicrobial agent, certain heterocyclic iodine-containing compounds termed broadly as dibenziodolium compounds, which are characterized in detail below.

Surface active compounds that have good cleansing power do not exhibit significant antimicrobial effectiveness as a rule. On the other hand, some cationic surface active agents such as quaternary ammonium compounds, for example, which do destroy certain types of bacteria, are inferior cleaning agents. As a consequence, in cleaning situations where substantial microbial control is a desired object, the conventional procedure calls for an ordinary washing step followed by a separate treatment of the surface being washed with an antimicrobial agent in a suitable physical form, such as a liquid or a powder.

It would be desirable and more efficient in many situations to combine both the cleansing and antimicrobial agents into a single composition in order to simultaneously perfrom the double function of cleansing and disinfecting. This has been attempted but has not been found completely satisfactory prior to this invention. One reason for previous failures, among others, has been the interference that occurs between a vast majority of antimicrobial agents on the one hand and soap and synthetic detergent compounds on the other. The incompatibility or interference manifests itself either in decreased washing power of the detergent surfactant or more generally, in partial or complete inhibition of the antimicrobial agent, or in both aspects.

Probably the best example of such interference is in compositions containing anionic detergent surface active agents, including soaps and non-soap compounds, and previously known antimicrobial agents. As a rule in such cases, the anionic detergent is less effective in its cleaning function than when used alone and the microbial control is substantially less than when the agent is used alone. Similiar interference commonly occurs in compositions containing nonionic, cationic and amphoteric surface active agents also.

A few compatible antimicrobial agents have become available recently which do impart some static or cidal action to soap and synthetic detergent systems against Gram positive bacteria such as Staphylococcus aureus', Bacterium ammoniagener, Lactolmcillus casei, etc. However, few, if any, antimicrobial agents are known which are compatible with, and impart significant antibacterial activity to soap and detergent systems against the more resistant Gram negative bacteria such as Escherichia coli, Proteus mirabilis, Pseudomonas aeruginosa, Salmonella choleraeszn's, etc.

Compatible antimicrobial agents are especially sought for use in detergent compositions which are to be used in laundering applications. In such situations it is desirable to have a residual amount of the disinfecting agent retained on the cloth in order to provide longer lasting effectiveness. The dibenziodolium compounds, described hereinafter, as a class have been discovered to possess such activity to a considerable degree.

In laundering situations, antimicrobial agents are '4/ a United States Patent 0 3,244,636 Patented Apr. 5, 1966 ice needed which can be used in a washing solution, remain on the fabric, and prevent multiplication of bacteria and/ or fungi and the development on the fabric of body odors. One advantage and application of such a treatment occurs in the washing of infants diapers, especially if the adherent antimicrobial agent is effective against Gram negative bacteria. Such bacteria attack nitrogen-containing compounds present in the materials with which the diapers are soiled forming ammonia. Thus, if the Gram negative bacteria are effectively destroyed, the unpleasant odor problems encountered in storing soiled diapers until they can be washed can be alleviated.

Most antimicrobial or germicidal agents are ineffective in a system containing chlorine-type bleaches. Trichlorocarbanilides and salicylanilides are good examples of agents which are destroyed by chlorine-type bleaches such as the widely used 5%% sodium hypochlorite solutions and potassium dichlorocyanurate-based dry bleaches. An unexpected advantage of the compositions of this invention is that they are stable in the presence of chlorinetype bleaches.

Antimicrobial agents which are compatible with soaps and synthetic detergents also find utility in the area of deodorant soap and cosmetic bars, i.e. toilet soaps. Here it is desirable for the active compound to exhibit substantivity to human skin so that the agent can be present to control the bacterial flora of the skin, which decomposes perspiration with concomitant odor development after a washing treatment.

Accordingly, it is an object of this invention to provide highly improved antimicrobial detergent compositions comprising a cleansing agent and an effective amount of a compatible heterocyclic iodine-containing antimicrobial agent. Another object is to provide an antimicrobial detergent composition which cleans effectively and is simultaneously capable of controlling a broad spectrum of Gram positive and, more especially, Gram negative organisms. Another object is to provide an antimicrobial detergent composition which may be used conjointly with and is effective in the presence of chlorine-type bleaches. A yet further object is to provide a new method of imparting antimicrobial properties to fabrics washed by the detergent compositions of this invention. Another object is to provide cotton and other fabrics having substantively distributed thereon an effective amount of an antimicrobial dibenziodolium compound deposited by a washing step employing an antimicrobial detergent composition of this invention ina manner described hereinafter. A still further object is to provide a so-called germicidal deodorant toilet soap bar comprising a cleansing agent and a minor but effective amount of the antimicrobial dibenziodolium compound.

It has been discovered that these and other objects are achieved by detergent compositions containing a cleansing agent and an effective amount of at least one dibenziodolium compound having the structure set forth below.

Dibenziodolium antimicrobial agents are compositions of matter having the following generic structural formula:

Formula I wherein R is selected from the group consisting of oxygen, sulfur, and --(CH,),,,-, m being an integer from 0 to 3; wherein Y and Y represent radicals selected from the group consisting of halogen, nitro, alkyl radicals containing up to 3 carbon atoms, halogen substituted alkyl radicals containing up to 3 carbon atoms, amino and sulfamyl, and Y and Y can be dissimilar;

n and n represent integers selected from the group consisting of 0, 1 and 2, and when n is 2, the Y radicals can be dissimilar and when n is 2 the Y radicals can be dissimilar and,

wherein X is selected from the group consisting of organic and inorganic anions.

R, Y, Y', X, n, n and m have consistent significance throughout the specification and claims.

The simplest type of the dibenziodolium compounds, i.e., where m and n are in the above formula and, what may be thought of as the parent compounds, contain a C 1 heterocyclic ring and no substituents on the phenylene rings. Such compounds are structurally represented by the following formula in which X is an anion:

Formula II The anionic portion, X, can be either an organic or inorganic anion. By way of examples, the following can be mentioned. Inorganic anions: sulfate, bisulfate, sulfite, iodide, chloride, bromide, phosphate, biphosphite, pyrophosphate, nitrate, nitrite and the like. Exemplary organic anions include acetate, propionate, decanoate, benzoate, substituted benzoate, phenylacetate, benzenesulfonate, substituted benzenesulfonate, fumarate, lactate, tartrate, citrate and the like. By selectively varying the anion, it is possible to adapt the dibenziodolium compounds to a variety of applications, due to the different physical and solubility characteristics of the different salt forms. Wide selection exists as to the anion, for the anion is not critical to the antimicrobial and compatibility characteristics of the compositions of this invention.

In the generic Formula I, where R can be an alkylenc group such as methylene, ethylene or propylene, the following nomenclature will apply: Methylene-containing compounds, dibenziodinium compounds; ethylene-containing compounds, dihydrodibenziodopinium compounds; propylene-containing compounds, dihydrodibenziodocinium compounds. These compounds have the following structural formula wherein m is 1, 2, or 3 respectively:

Formula III The heterocyclic ring can contain an oxygen atom or a sulfur atom in place of methylene, ethylene and propylene along with iodine and carbon. Such compounds are referred to respectively as dibenzoxiodinium compounds having the following structural formula:

Formula IV and dibenzthiaiodinium compounds having the following structural formula:

Formula V In depicting the alkylene-derivatives and the oxygen and sulfur derivatives in the above structural formulas, it should be understood that Y and Y,,' are comprised as indicated in the generic structural representation,

For the sake of clarity, the term dibenziodolium is used in the description of this invention in its broadest sense to include each of the specific compound forms illustrated above. It has been discovered that the beneficial characteristics described in this invention are possessed according to varying degrees by all of the compounds falling within the above structural formulas.

Typical of the antimicrobial compounds contemplated by this invention include:

Bis(dibenziodolium)sulfate Dibenziodolium bisulfate Dibenziodolium lactate Bis(2,4-dichlorodibenziodolium sulfate Bis (Z-chlorodibenziodolium) sulfate Bis 3-chlorodibenziodoli urn) sulfate 3,7-dichlorol O-H-dibenz (be iodinium hisulf ate dihydrate 2,4-dibromodibenziodolium bisulfate 2-bromodibenziodolium lactate Bis 3,7-difiuorodibenziodolium sulfate 3,7-dibromo-l0,1l-dihydrodibenz(be)iodepinium dihydrogen phosphate Bis 3-nitrodibenziodolium sulfate 3,7-dinitro-1 O-H-dibenz be iodinium bisulf ate 3,7-dinitrodibenz(be) (1,4 oxiodinium bisulfate Bis 3 ,7-dinitrodibenziodolium sulfate Bis 2-nitrodibenziodoliurn sulfate 3-chloro-7-nitrodibenz be) (1,4 oxiodinium bisulfate Bis 3-chloro-7-nitrodibenz be) (1,4 oxiodinium] sulfate 3,7-bis trifluoromethyl dibenziodolium iodide Dibenziodolium 2,4,5-trichlorophenate 2,4-diethoxydibenziodolium citrate 3,7-dinitrodibenziodolium benzoate 3,7-propyldibenziodolium acetate 2-fluoro- 1 0-H-dibenz( be iodinium fluoride Z-(perfluoromethyl)dibenziodolium bromide 2-iodo-11,1Z-dihydro-10-H-dibenz(be)iodocinium phenate Bis 3-chlorodibenziodolium monohydrogen phosphate 3-chloro-10,1 1-dihydrodibenz(be)iodepinium dihydrogen phosphate Bis 3 ,7-dichlorodibenziodolium sulfate 3,7-dinitrodibenz(be) (1,4 oxiodinium bisulfate 3,7-disulfamoyldibenz (be) (1,4) oxiodinium bisulfate 1,3-dich1oro-7-nitrodibenz( be) (1,4 oxiodinium bisulf ate Bis 1 ,3-di chloro-7-nitrodibenz (be) (1,4)

oxiodinium] sulfate 3,7-dinitrodibenz be) (1,4) oxiodinium lactate 3-bromo-7-nitrodibenz( be) (1,4 oxiodinium bisulfate Bis [dibenz (be) 1,4) oxiodinium sulfate 3,7-diaminodibenz be) (1,4) oxiodinium iodide 1-chloro-3,7-diaminodibenz be) (1,4) oxiodinium bisulfate Bis 3 ,7-dichlorodibenz (be) 1,4 oxiodinium sulfate 3 ,7-dibromodibenz( be) (1,4 oxiodinium chloride 3-chlorodibenz(be) (1,4 oxiodinium chloride 2-chlorodibenz be) (1,4 oxiodinium bromide 3,7-diethy1dibenz(be) (1,4 oxiodinium chloride 1,3-dichlorodibenz be) (1,4 oxiodinium chloride 2,3-dichlorodibenz (be( 1,4 oxiodinium bromide l-chlorodibenz (be) (1,4 oxiodinium chloride 4-nitrodibenz( be) (1,4)thiaiodinium bisulfate 4,6-diamino (be) (1,4) thiaiodinium nitrate The precise method by which any of these compounds can be prepared constitutes no part of this invention. Several alternate methods are available for the preparation of the compounds representative of Formula 1 above. One of the known synthesis routes of such compounds is a two-step process set forth in Reaction A below.

According to the following reaction, o-iodobiphenyl or o-iodobiphenyl alkane (V1) is oxidized with peracetic acid to yield the corresponding iodoso acetate compound (VH). This compound is reacted with sulfuric acid and thus reduced to a heterocyclic dibenziodolium compound bial activity to a broad spectrum of detergent surfactant compositions. Due to the cationic nature of the dibenziodolium compounds, it was confidently expected that incompatibilties might exist with anionic and amphoteric detergent surface active agents. Contrary to expectations, it was found that the dibenziodolium compounds can be used with excellent results in combination with anionic and amphoteric detergent surfactants.

This brings out the point that the state of this art has simply not advanced to the stage where one can predict with any degree of certainty how a given antimicrobial agent will behave in a detergency system. Some of the numerous unknown or variable factors which can have some effect upon the performance of the agent include the complex nature of the detergent compositions themselves, the soil encountered, the different types of fabrics involved, the different ionic characteristics of the compounds, the dilferences in aqueous solutions and the like. Based solely on their respective ionic characteristics, it might have been expected that the cationic dibenziodolium compounds of this invention would be compatible with nonionic detergent based systems. Surprisingly, that does not happen to be the case. The interference between such materials ranges from substantial inhibition of the dibenziodolium compounds to complete inactivation of their antimicrobial properties.

Also surprising is the control which the dibenziodolium compounds exhibit over the Gram negative type species even when combined in a detergent composition. This, of course, was totally unexpected in view of recent confirmed findings that Gram negative organisms have different physiological characteristics from Gram positive organisms. It is now possible, therefore, according to this invention, to render soap and synthetic detergent compositions germicidally active. Such compositions protect laundered fabrics against a wide variety of Gram positive and Gram negative bacteria. In addition, the compositions of this invention are effective against a large number of yeast and fungus organisms which are known to cause infections of the skin and mucous membranes.

Relatively small amounts of the dibenziodolium antimicrobial agents are sufficient to render the detergent compositions germicidal. Amounts as low as 0.01% based on the weight of the detergent composition have proved satisfactory in some cases. The preferred concentration range, however, is from 0.05% to 4% by weight of the synthetic detergent or soap composition used. The upper limit will generally be determined by practical considerations such as economics and desired solubility characteristics. Usage levels as high as 10% by weight of the detergent composition can be used to advantage. As a general rule, increasing the concentration of the agent increases the antimicrobial effectiveness of the composition.

Anionic organic detergents which can be used in the composition of this invention, if desired, include both the soap and non-soap variety. The term soaps as used herein is meant to designate alkali metal soaps such as sodium and potassium salts of the higher fatty acids of naturally occurring plant or animal esters, e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils, grease and lard, and mixtures thereof. Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutraliza tion of the fatty acids which are prepared in a separate manufacturing process.

Examples of suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.

Examples of anionic organic non-soap detergents include those broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. Included in the term alkyl is the alkyl portion of higher acyl radicals.

Important examples of the synthetic non-soap detergents which form a part of the preferred compositions of the present invention are the sodium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C -C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkylbenzenesulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms in a straight or branched chain, for example, those of the types described in United States Letters Patents Nos. 2,220,099 and 2,477,383; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglycerides sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol, e.g., tallow or coconut oil alcohols, and about 1 to 6 moles of ethylene oxide, sodium or potassium salts of alkylphenol ethylene oxide ether sulfate with about 1 to about 10 units of ethylene oxide ether per molecule and in which the alkyl radicals contain about 9 to 12 carbon atoms; the reaction product of fatty acids esten'fied with isethionic acid and neutralized with sodium hydroxide, where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyltauride in which the fatty acids, for example, are derived from coconut oil, and others known in the art, a number being specifically set forth in United States Letters Patents Nos. 2,486,921, 2,486,922 and 2,396,278.

The amphoteric synthetic detergents which can be used within by this invention can broadly be described as derivatives of aliphatic amines which contain a long chain of about 8 to about 18 carbon atoms, and an anionic water-solubilizing group, e.g., carboxyl, sulfo, sulfato. Examples of compounds falling within this definition are sodium-3dodecylaminopropanesulfonate and sodium-3- dodecylaminopropionate. I Zwitterionic surface active compounds which are structurally similar to the amphoterics as just described are intended to be covered by that term in this invention. Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium compounds, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic watersolubilizing group, e.g., carboxy, sulfo, or sulfato. Examples of compounds falling within the definition are 3- (N,N dimethyl N hexadecylammonio) propane-1- sulfonate (APS) and 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy-propane-l-sulfonate (HAPS). The antimicrobial efiectiveness of representative dibenziodolium compounds can be observed from Table I where bacteriostatic assay results are presented. These figures were obtained by means of a Standard Tube Dilution Test" which consists essentially of preparing serial dilutions of the antibacterial compositions to be tested in an FDA broth medium, inoculating with the chosen test organism and observing the minimum concentration which ust prevents growth of the organism throughout incubation. This minimum concentration is called the bacteriostatic breakpoint.

In these in vitro tests, two types of organisms were used, including Staphylococcus aureus FDA 209 and Escherichia coli. The aureau organism is Gram positive and the coli is a Gram negative species.

Subsequent to the serial dilution of the antimicrobial agent, 0.1 ml. of the organism (10" cells) is added to the tube containing the agent after which the tube is incubated for 24 hours at 37 C., and thereafter the bacteriostatic breakpoint is determined turbidometrically.

in the form of a sulfate salt (I). the compositions of this invention.

REACTION A R Peracetic R Yn Yn' Ya Yn' 1 acid IO Formula V I Formula V II This salt is useful in Formula I wherein R, Y, Y, n and n have the same significance defined earlier, and X is sulfate or bisulfate.

Another method is available for the synthesis of dibenziodolium sulfates and related heterocyclic iodine compounds which differs from Reaction A above by avoiding the use of peracetic acid and its known dangers. This alternative route proceeds according to Reaction In Reaction B above, each substituent has the same significance as defined earlier and X is sulfate or bisulfate.

According to Reaction B, the iodo starting material of Reaction A (VI) is chlorinated t form the iodo dichloride compound (VIII). Treatment of the iodo dichloride with alkali yields the corresponding iodoso compound (VII) which can in turn be transformed to the desired heterocyclic dibenziodolium compound (I) by treatment with sulfuric acid or other strong Lewis acid.

Yet another method, amply illustrated in the prior art, is available for the preparation of the dibenziodolium iodides and related heterocyclic iodine compounds. According to this procedure, an o,o-diaminobiphenyl is diazotized to yield a tetrazonium salt, which, when decomposed in the presence of an aqueous solution of potassium iodide, yields a dibenziodolium iodide. Other iodine-containing ring systems represented by the above formulas are prepared in analogous fashion from the corresponding diamino starting material.

Reactions A and B, above, yield as their final product a sulfate or bisulfate salt. Other salts can be prepared from the above salts by methods well known to the art, such as a metathetic reaction. For example, an aqueous solution of bis(dibenziodolium)sulfate can be treated with an aqueous solution of barium chloride or barium nitrate to form dibenziodolium nitrate or chloride and a readily separable insoluble precipitate of barium sulphate. Alternatively, barium hydroxide can be reacted with bis(dibenziodoliurn)sulfate to yield an insoluble precipitate of barium sulphate plus a solution of dibenziodolium hydroxide. Neutralization of the hydroxide with any suitable acid yields a dibenziodolium salt in which the anion of the acid becomes the anion 0f the dibenziodolium salt.

Certain of the compounds preparable by either of the above procedures may not be sufficiently soluble in water for a specific desired purpose. In that event, resort can be had to a more soluble group of salts wherein the cationic portion is as above illustrated and the anion is derived from an a-hydroxy carboxylic acid or dicarboxylic acid; for example, lactic, citric, gluconic, glucoheptonic, and tartaric acids. Such compounds can be represented by the following formula which is the same as Formula I except that the anionic substituent X has a specific definition as set forth below:

corresponds to X in Formula I, Y, Y, R, n and n are as previously described and R" is hydrogen, lower alkyl, or hydroxy lower alkyl; R" is lower alkyl, lower alkenyl, carboxy-substituted lower alkyl, or a-hydroxy carboxy-substituted lower alkyl.

This group of salts can be prepared in the same manner as outlined above except that lactic, tartaric, or citric acid is used to neutralize the dibenziodolium hydroxide, dibenziodinium hydroxide, dihydrodibenziodepinium hydroxide, or dihydrodibenziodocinium hydroxide.

The oxygen and sulfur derivatives as exemplified respectively by Formulas IV and V can be prepared by tetra-azotizing a suitably substituted 2,2'-diamino-diphenyl oxide or 2,2-diamino-diphenylsulfide and then decomposing the tetra-azoate in the presence of an iodide salt. A preferable method, however, for the preparation of the oxygen and sulfur compounds involves the direct iodination of a suitably substituted diphenyl ether or diphenyl sulfide using iodosyl sulfate in sulfuric acid solution as the iodinating reagent. The product of this reaction is usually a dibenz(be)( 1,4)oxiodinium or thiaiodinium bisulfate. Recrystallization of the bisulfate salt from water usually serves to convert it to the corresponding sulfate salt.

Another method is available for the preparation of oxygen derivatives represented by Formula IV. According to this procedure, a suitably substituted 2-iododiphenyl ether is reacted with peracetic acid to give the corresponding iodoso acetate compound, which can then be cyclized in the presence of concentrated sulfuric acid to yield, usually, the bisulfate salt of the desired dibenzoxiodinium compound.

As mentioned previously, the various dibenzoxiodinium and dibenzthiaiodinium salts which are prodced by any of the above three reactions can be transformed to other salts by standard metathetic processes. For example, a sulfate salt can be dissolved in water and treated with a large excess of sodium chloride to yield the corresponding chloride, or with a large excess of sodium nitrate to yield the corresponding nitrate. Other methods of preparing salts of the dibenzoxiodinium or dibenzthiaiodinium compounds of this invention will be readily apparent to those skilled in the art.

It has been discovered unexpectedly that the dibenziodolium compounds described above impart antimicrowherein Table I shows that the dibenziodolium compounds retain their antimicrobial properties in the presence of representative soap and non-soap anionic detergents and amphoteric detergent surfactanats. This was discovered by modifying the above assay procedure by the addition of subinhibitory concentrations of the surface active agents to the prepared tubes before the addition of the test organism. The typical anionic surface active agent selected was alkyl benzene sulfonate (ABS) in which the alkyl substitutent is a dodecyl group derived from tetrapropylene. The soap tested was 80:20 mixture of sodium tallow and coconut oil soap. The representative amphoteric surface active compound was 3-(hexadecyldimethylammonio -2-hydroxypropane-l-sulfonate HAPS) In tests with Staphylococcus aureus the subinhibitory level of ABS and HAPS was 12.5 parts per million. With Escherichia coli the level of ABS where indicated in the footnotes was 50 parts per million, and HAPS was 12.5 parts per million. The soap was present in both series of tests in amounts of 50 parts per million.

Dashes at certain points in Table I indicate that no tests were run. The retention of marked antimicrobial effectiveness by the cationic antimicrobial dibenziodolium compounds in the presence of an anionic and amphoteric surfactant is well demonstrated.

TABLE I BACTERIOSTATIC BREAKPOIN'IS IN MICROGRAMS PER MILLILITER Organism Iodolium compound Slaphylo- Eschericoccus chin coli aumts Bis (dibenziodolium) sulfate, alone 3. 75 3.13 with u ABS 6. 25 l 6. 25 Dlbenzlodolium bisulfate, alone 6.25 12. with ABS 6. 25 1 12. 5 Bis (3-nitrodibenziodolium) sulfate, alone 47 1 .12 with Cu ABS 2-3 5 with HAPS.. 1 5 3,7dinitrodibenz(be) (1,4)oxiod1nium bisultate. alone 35 50 with C11 ABS- -15 15-20 with Soap 2 -25 1 -35 with HAPS 5 50 3-chl0ro-7-nitrodibenz (be) (1,4 )oxi 15 50 5 20-25 5-10 3 -40 with HAPS 5 Bis (2-nitrodibenziodolium) sulfate, alone. 10 10 with C11 ABS.- l-2 10 with $08 9-10 10 with HAPS 10 3,2(1bis-trifiuoromethyl) 1 15 5 50 2 3-5 1 50 5 5-10 1. 2. 4 with Cu ABS 0. 78 2. 4 2-chlorodibenz (be) (1,4)

alone 2. 4 1. 57 with C1: ABS 1.2 2.4 3,7-dimethyldibenz(be) (1,4) oxiodiruum chloride, alone 2. 4 3. 13 with Cu AB 1. 56 3.13 1,3'dieh1orodibenz(be) (1 o ride, 2. 4 6. 2a with Cu ABS 1.2 6.25 2,3-dichlorodibenz(be) (1,4) oxiodmlum chloride, alone 0. 78 6. 25 with C1; ABS 0. 78 6. 25 1-chlorodibenz(be) (1,4)oxiodimum chloride,

alone 1. 2 1. 2 with Cu ABS 0. 6 2. 4

1 C ABS present in these experiments at 50 parts per million. I Soap present in these experiments at 50 parts per million.

Test described in an article authored by Herbert Quinn appearing in Applied Microbiology (January 1962, pages 74-78). This test revealed the further surprising discovery that the dibenziodolium compounds are substantive to cloth fabrics such as cotton even from detergency systems. This illustrates an important application for the compositions of this invention, namely, antimicrobial textile finishes, as discussed above. Briefly, the Cloth Protection Test consists of washing cloth swatches in an aqueous solution containing a detergent composition and the antimicrobial agents to be tested, drying the swatches in a microorganism free atmosphere, and then inoculating the dried swatch with 0.1 ml. of a suspension of test organism in 5% serum (0.1 ml. containing approximately 5000 organisms). After the inoculation with the serum suspension, the swatches are again allowed to dry and then they are planted in an agar medium Petri plate with the inoculated surface facing up and an overlay of nutrient is carefully applied over the fabric. The Petri plates are then incubated at 37 C. for 48 hours, after which bacterial counts are taken by means of a low power binocular microscope. The relative ability of a treated fabric to inhibit growth or kill the organism is the measure of the effectiveness of a particular agent or mixtures of agents being tetsed. In Tables 11, 111 and IV where these experimental results are given, the lower number of colonies counted indicates the relative greater antimicrobial control of the organism as compared to a control figure obtained without one of the agents. Each figure represents an average of the colonies counted on six replicate cloth swatches.

The standardized detergent composition employed in these tests consisted of the following ingredients on a weight basis:

Percent Dodecylbenzenesulfonate 17.5 Sodium tripolyphosphate 50.0 Sodium sulfate 7.2 Sodium silicate 12.8 Water 12.5

The composition was used at a concentration of .25% by weight of the washing solution. The temperature of the washing solution was F. and contained 7 grains of hardness. The antimicrobial agent was used at the percentage levels indicated in the tables. All percentages are on a weight basis and the percent of the dibenziodolium is based on weight of the total detergent composition.

In Tables II, III, and IV, a zero figure indicates a virtually antiseptic condition or complete control of the microorganism. The fact that such significantly low levels of the dibenziodolium compounds which are cationic offer this remarkable degree of control from a cleansing formulation containing an anionic detergent surfactant was completely unexpected. Moreover, the cleaning performance of the compositions of this invention was comparable to results obtained using detergent compositions which do not contain dibenziodolium antimicrobial compounds.

In Table II it will be seen that virtually complete control was obtained against the Gram positive aurcus species by each of the dibenziodolium compounds with at least one of the concentration levels tested. In several cases, such as 3,7-dinitro-l0-H-dibenz(be)iodinium bisulfate, 3-chloro-7-nitrodibenz(be) (1,4)oxiodinium bisulfate and dibenziodolium bisulfate, the virtually complete control was obtained at a very low level of .1% by weight of the agent. It is remarkable that the Gram negative organisms were completely controlled by each of the dibenziodium compounds under the test conditions with amounts of 2 to 4 percent of the agents. Especially outstanding control of Escherichia coli was seen with 3,7-dinitro-l0-H-dibenz(be)iodinium bisulfate, 3-chloro-7-nitrodibenz(be)(1,4)oxiodinium bisulfate and bis(3-nitrodibenziodolium)sulfate. The control obtained at the low levels of usage was completely unexpected. Generally, increasing the concentration of the active dibenziodolium agents results in greater microbial control. Thus, within the practical limits of economics and intended use, the detergency compositions of this invention have very broad applications in instances where control of Gram positive and Gram negative organisms on fabrics is desired or necessary.

Additional Cloth Protection Tests were conducted, in some of which a chlorine bleach was added to the wash water along with the detergent composition and a specific antimicrobial agent. When bleach was used in the laundering process, it was added at a level of 200 parts per million of available chlorine. As mentioned previously this level of chlorine would destroy or inactivate such well known germicidal agents as trichlorocarbanilides and halogenated salicylanilides. However, it was surprisingly discovered that the compositions of this invention could satisfactorily be used conjointly and in admixture with active chlorine-containing compounds, preferably at levels which provide from about .5% to about 50% available chlorine. Five and one-fourth percent aqueous solution of sodium hypochlorite was used as the representative chlorine bleach, although similar results are obtained with dry, solid water-soluble chlorine bleaching compositions. Examples of such powdered bleaching agents Table IV illustrates the unexpected discovery that the antibacterial detergent compositions of this invention are effective even in the presence of chlorine bleaching agents. This is evidenced by the fact that the colony counts obtained when the bleaching agent was used are uniformly less than the Control Figure obtained when no bleaching agent was used. lncidentially, the chlorine bleaching agent makes no contribution to the control of the organism since the inoculation of the cloth occurs after the washing cycle and the chlorine is not significantly substantive to the cloth. The dashes in certain spaces indicate no such tests were conducted.

The behavior of dibenziodolium compounds and other anionic detergent surfactants was evaluated in a similar manner and these data are presented in Table V. For this evaluation, the dibenziodolium compound selected being representative of the broad class of di'benziodoliums was dibenziodolium sulfate, corresponding to Formula II above.

The detergent composition used in Table V was exactly as described previously and was used at the same concentration in the washing solution. Where a one-toone detergent surfactant mixture was tested in place of a sole detergent surfactant, the mixture was present at 17.5% by weight in the compositions. By virtue of the one-to-one ratio, each surfactant was used at an 8.75% by weight level.

Table II.-Clth Protection Test Dibenzio- 3-chloro-7- dolium com- 3,7-dinitro Dibenzionitrodibenz- Bis(3-nitro- Bis(2-chloro- Test organism pound as Control lO-H-dibeuzdolium (be) (1,4)oxidibenziodibenziopereent of figure (be) iodinium bisulfate odinium dolium) dolium) detergent bisulfate bisulfate sulfate sulfate composition 4 0 0 0 2 0 O 0 0 0 1 0 0 0 26 0 Staphylococcus aureus FDA 0.5 0 0 0 240 14 209 0. 25 0 0 0 880 1, 090 3.?) 2, 630 2, 500 2,025 2,100 2, 540 4 (l 0 0 2 0 0 0 0 0 1 0 o 0 Eschmchm coli 0. 5 O 285 0 0 140 0.25 46 1,050 0 0 1, 460 8(1) 2, 490 2, 630 545 1, 400 3, 585

are dichlorocyanuric acid and the sodium and potassium salts thereof; trichlorocyanuric acid; 1,3-dichloro-5,5-dimethyl hydantoin; N,N'-dichlorobenzoylene urea; paratoluene sulfondichloroamide; trichloromelamine; N-chloroammeline; N-chlorosuccinimide; N,N'-dichloroazodicarbonamidine; N-chloroacetyl urea; N,N'-dichlorobiuret; chlorinated dicyandiamide; sodium hypochlorite; calcium hypochlorite; lithium hypochlorite; chlorinated trisodium phosphate. In the experiments presented in Tables III and IV, the conditions were as previously set forth, namely, the detergent composition was used at a concentration level of on a weight basis and the temperature of the wash water which contained 7 grains of hardness was 140 F. The concentration of the antimicrobial agent was .1% on a weight basis in each instance. These tests were expanded to include four antimicrobial agents, one Gram positive species and three Gram negative species.

It will be noted from examining Table III that virtually no interference was encountered between any of the several agents tested and the anionic surfactant in the standardized detergency composition. These results serve to emphasize the surprising compatibility found to exist between the cationic antimicrobial agents and anionic detergent surfactants.

TABLE III.--CLOTH PROTECTION TEST Test organism Antimicrobial agent at .1%

by weight concentration Staphylo- Pseudococcus Eschermonaa Proteus aureus ichia colt aeruglmirabilia nota BsQ-nitrodibenziodolium) sulfate 980 0 1, 0 Bis(dibenz(be) (1,4)oxiodinium)sul ate 1, 470 3,210 820 0 a-chlorodibenz (be) (1,4) 0x10- dtm'um chloride 250 2, 550 3, 120 340 2'chlorodibenz (be) (1,4) oniodinium chloride 2, 840 230 0 3,7-dimethyldibenz (1,4)

oxiodinium chloride 1, 270 1, 650 3, 040 1,3-dichlorodlhenz (be) (1.4)

oxiodinium chloride 3, 480 3, 330 3, 250 2, 240 2,3dichlorodibenz (be) (1,4)

oxiodinium chloride 3, 890 3, 110 3, 010 600 1-eh1or0dibenz( )(l,4) oxiodinium chloride. 3, 930 210 0 Control figure 3, 910 3, 580 3, 420 2, 300

TABLE IV.--CLOTH PROTECTION TEST Test organisms Antimicrobial agent Staphylococcus aareur Escherichia coli Pacudomonu acruginosa Proteus mimbilis Bleach No bleach Bleach No bleach Bleach No bleach Bleach No bleach Bis(2-chlorodibenziodolium)sulfate 710 4, 280 2, 030 130 Dibenziodoliurn lactate 1, 030 4, 700 1, 510 170 3 chloro 7-nitrodibenz (be) (1, 4) oxiodinium bisuliate 1, 350 2, 690 1, 740 200 Bis(2-nitrodibenziodolium )sultatc 0 490 0 3,7 disuliamoyldibenz (be) (1, 4) oxiodinium bisultate 2, 680 1, 760 4, 930 4, 680 1, 680 1, 440 560 450 1,3 dichloro 7-nitr0dibenz(be) (1,4)0xi0dinium bisuliate 2, 480 1, 120 4. 760 4, 370 1, 660 1, 490 450 670 3 brorno nitrodibenz (be) (1, 4) oxiodinium bisulfate 2, 380 1, 260 4, 230 780 1, 700 1,890 320 93 Bis(dibenz(bc) (1,4) oxiodinium) sulfate 2, 240 1, 430 4, 620 4, 230 0 260 37 0 3,7-diaminodibenz (be) (1,4) oxiodinium iodide.. 2,070 1, 630 4, 310 3, 890 1, 640 1, 790 560 520 Bis(3,7 dichlorodibenz(be)(1,4)oxiodinium) sulfate 1, 700 1. 040 4, 060 4,170 1, 700 l, 920 19 0 8,7-dibromodibenz(be) (1,4) oxiodinium chloride... 1, 600 1, 320 5,880 4, 980 1,550 1, 850 37 19 3-chlorodibenz(be) (1,4)0xiodinium chloride l, 510 970 4, 450 5, 260 1,870 1, 830 300 150 Control figure 3, 040 0 0 900 5, 900 1, 850 1,850 620 620 TABLE V Dibenziodoliurn Anionic surfactants sulfate as Organism percent detergent C ABS CNAS 2 AGS CnABSzTAS 4 composition Staphylococcus auteur 2 1 340 2. 520 950 0. 0 900 2, 400 2, 500 2, 300 Escherichia coli 2 0 0 240 20 0.0 2, 900 2, 600 2, 500 1, 900

l Pcntadecylbenzene suli'onatc, in which the alkyl suhstituent is derived irom pentapropylene. 1 Coconut alkyl sulfate containing an average of 12 carbon atoms per molecule.

' Alkyl glyoeryl ether sulionate derived from coconut oil.

One-to-one mixture and tallow alkyl sulfate.

Excellent antimicrobial activity and at times antimicrobial enhancement is obtained with mixtures of dibenziodolium compounds and anionic and amphoteric surfactants respectively. Such enchancement is notably obtained with the class of amphoteric surfactants comprising 3-(N,N- dimethyl-N-alkylammonio)-propane-1-sulfonate and 3- (N,N dimethyl-N-alkylammino)-2-hydroxy-propane-1- sulfonate, wherein the alkyl radical contains from 12 to 18 carbon atoms. This discovery is demonstrated below by bactericidal assay determinations using as representative anionic surface active agent, dodecyl benzene sulfonate, and 3 (hexadecyldimethylammino)-2-hydroxy-propanel-sulfonate (HAPS) as a typical amphoteric surfactant. Both have been described previously. The results obtained with ABS appear in Table VI and with HAPS in Table VII.

The bactericidal assay test used in this series was carried out by determining the percent kill of typical organisms by exposing a suspension of bacteria to a desired test agent, removing aliquots of the treated suspension at a specified time interval and inoculating onto a 5% serum-agar plate, and thereafter incubating the agar plate 24-48 hours and noting the number of bacterial colonies which develop.

Specifically, this series of tests was carried out by determining the percent kill of Staphylococcus aureus FDA 209 and Escherichia coli in a matrix with an exposure time of 10 minutes to a predetermined concentration of the antimicrobial agent. The suspending medium was FDA nutrient broth, and the inoculum size was approximately 500,000 cells/ml. One-tenth milliliter of the suspension was removed after the 10-minute exposure and placed in 9.9. ml. of 0.1% peptone water. One-tenth ml. of the diluted suspension was plated into Trypticasesoy Agar and allowed to incubate for 24-48 hours at 37 C. Colonies were then counted and the percent reduction in viable count was determined in relation to a colony of dodecylbenzcnc sulionate, the dodecyl substituent derived from tetrapropylcnc,

count attained by plating the inoculated broth without an active agent.

TABLE VI.-BACTERICIDAL ASSAY PERCENT REDUCTION IN COLONY COUNT Antimicrobial compound 1 Broth, SA. ABS, SJ.)

Dibenziodolium bisuliate 0 3-chlorodibenz(be)(l,4) oxiodinium chloride... 72 72 2-chlorodibenz(be)(1,4) oxiodinium chloride 10 99 3,7-dimethyldibenz (be) (1,4) oxiodinium chloride 0 1,3'dichlorodibenz (be) (1,4)oxiodinium chlpri e 0 77 2,3-dichlorodibenz(be) (1,4)oxiodinium chloride 0 98 1-chlorodibenz(be) (1,4)oriodinium chloride 30 99 Matria 30 60 1 Used at a concentration of 50 mtg/ml. I Used at a concentration of 100 meg/ml. Staphylococcus aureus FDA 209.

TABLE VII.BACTERICIDAL ASSAY PERCENT 1 Used at a concentration of 10 mcgJml. 1 Used at a concentration of 20 mcg./ml. Staphylococcus aureua FDA 209.

4 Eacherichia coli.

The figures in Table VI and VII show that a broad range of activity is achieved between the dibenziodolium compounds and anionic and amphoteric detergent compounds. The markedenhanced activity apparent from Tables VI and VII was completely unexpected. Apparently there is an unexplainable favorable interaction between detergent compounds, the antimicrobal agents and the microorganisms.

While excellent results are generally obtained with any of the several types of dibenziodolium compounds previously described in detail, the preferred compounds according to this invention are the dibenzoxiodinium compounds corresponding to Formula IV above. Especially preferable are the chloro-derivatives such as bis(3,7-dichlorodibenz(be)(l,4)oxiodinium)sulfate, 3 chlorodibenz(be)(1,4)oxiodinium chloride, 2 chlorodibenz(be) (1,4)oxiodinium chloride, and l chlorodibenz(be)(1,4) oxiodinium chloride. The unsubstituted species, dibenz- (be) (l,4)oxiodinium chloride, also is preferred.

The dibenziodolium compounds have been found compatible with the above identified soaps and non-soap synthetic detergent compositions in bar, liquid, flake, granular, and other built or unbuilt forms and can be incorporated into the soap or detergent composition by any suitable method which preferably yields as a result a uniform distribution of agents throughout the whole mass.

The detergent compositions of this invention can contain any of the usual adjuvants, diluents, and additives, for example, builders, perfumes, anti-tarnishing agents, anti-redeposition agents, dyes, fluorescers, suds builders, suds depressors as well as cationic synthetic detergent surfactants, without detracting from the advantageous properties of the compositions.

Regular use of a toilet soap bar containing 1.0% of a suitable dibenziodolium compound of this invention such as 3,7-dinitrodibenz(be)(1,4)oxiodinium bisulfate, bis- (2-nitrodibenziodolium)sulfate, or bis(3-nitrodibenziodolium)sulfate, results in substantial reduction in bacterial population of the skin and thereby markedly reduces body odor attributable to the bacterial degradation of perspiration. (Such bars can comprise well known mixtures of sodium tallow and coconut oil soap in ratios ranging from 50:50 to 90:10 tallowzcoconut oil.)

The following examples are offered as being merely illustrative of how this invention can be carried out in practice. The invention is not restricted to these examples since the broad scope of this invention is readily apparent.

Example 1 A sample formula for a milled toilet detergent bar which can be prepared by means known and used in the art is as follows: (The term middle cut as used herein refers to that fraction of distilled coconut alcohol which consists of predominantly lauryl and myristyl alcohols.)

acids 19 Sodium chloride 6 Moisture 9 Bis(3,7-dichlorodibenz(be) (1,4)oxiodinium sulfate 1 This bar cleanses well and exhibits good odor reducing properties evidencing antimicrobial effectiveness. It reduces the number of bacteria on the skin and does not discolor significantly.

Example 2 A granular built synthetic detergent composition having 16 the following formulation can be prepared and the antimicrobial agents of this invention can be incorporated therein. The composition, in addition to performing well in its cleaning capacity, imparts considerable antimicrobial activity to fabrics cleansed in the solution.

Percent Sodium alkyl benzene sulfonate (the alkyl radical averaging about 12 carbon atoms and being derived from propylene) 17.5 Sodium tripolyphosphate 50.0 Sodium sulfate 14.0 Sodium silicate 7.0 Bis(2-chlorodibenziodolium)sulfate 1.5 Water 10.0

Example 3 An excellent antimicrobial granular detergent composition has the following formula:

Percent Sodium salt of p-dodecylsulfonylphenol 17.5 Sodium sulfate 23.0 Sodium tripolyphosphate 49.0 Sodium silicate 6.0

Water 3.5 Dibenz(be)(1,4)oxiodinium chloride 1.0

A water solution containing from 0.15 to 0.45% concentrations of the above formula provides very good cleaning results in both laundering and dishwashing situations, while controlling bacteria.

Example 4 The following composition containing an effective bleaching agent performs very well in cleaning and disinfecting capacities:

Percent Tallow alkyl sulfate 10.0 Sodium dodecylbenzenesulfonate (the dodecyl group being derived from tetrapropylene) 10.0 Sodium tn'polyphosphate 49.0 Sodium sulfate 10.0 Potassium dichlorocyanurate 20.0 3-chlorodibenz(-be)(1,4)oxiodinium chloride 1.0

Example 5 An excellent built liquid laundering composition which cleans as it disinfects and which is suitable for any household cleaning situation can have the following composi- An excellent built liquid detergent com-position accordmg to this invention has the following composition:

Percent Sodium dodecylbenzenesulfonate (the dodecyl group radical being a straight chain aliphatic radical averaging 12 carbon atoms) 12.0 Trisodinm ethaned-hydroxy-l,l-diphosphonate 20.0

Potassium toluene sulfonate 8.0 Sodium silicate (ratio SiO :Na O of 2.45:1) 3.8 Carboxymethyl cellulose 3.0 3 chloro 7 nitrodibenz(be)(l,4)oxiodinium bisulfate 2.0

Water Balance The performance of this antimicrobial detergent composition is excellent in laundry tests as well as dishwash- 17 ing evaluations from the cleaning and sanitizing point of view.

Example 7 An excellent household scouring cleanser can contain the following ingredients:

Percent Silica flour (abrasive) 84.5 Detergent consisting of 85% trisodium phosphate and dimethyl coconut ammonio acetate 14.0 Lithium hypochlorite .5 Dibenziodolium bisulfate 1.0

This composition disinfects as it cleans and can be usefully employed in kitchen and bathroom situations.

Example 8 An effective antimicrobial granular detergent composition has the following formulation:

Percent Sodium dodecylbenzenesulfonate (dodecyl group rerived from tetrapropylene) Tallow alkyl sulfate 2.0 Hydrogenated marine oil fatty acid 2.2 Sodium tripolyphosphate 59.6

Sodium silicate (ratio SiO :Na O of 2:1) 9.7 Sodium sulfate 13.5 1-chlorodibenz(be)(1,4)oxiodinium chloride .5 Water Balance Example 9 Another highly effective granular detergent has the following composition:

Example 10 An antimicrobial laundering composition especially effective at cool water temperatures has the following composition:

Percent 3 (N,N dimethyl-N-hexadecylammonio)-2-hydroxy-propane-l-sulfonate 12.0 Sodium tripolyphosphate 20.0 Sodium silicate (SiO :N-a O=1.6: 1) 3.8 Potassium toluene sulfonate 8.5 Sodium carboxymethyl hydroxyethyl cellulose .3 Fluorescent dye .12 Perfume .15 Benzotriazole .02 1,3 dichloro 7 nitrodibenz(be)(1,4)oxiodinium bisulfate 3.0 Water 52.11

Example 11 Another effective antimicrobial cool water built granular composition according to this invention has the following composition:

Percent 3 (N,N dimethyl-N-hexadecylammonio)propanel-sulfonate 17.0 Trisodium ethane-1-hydroxyl-l,l-diphosphonate 45.0 3,7-dinitrodibenz(be)(1,4)oxiodinium lactate 4.0

Sodium silicate (Na O:SiO =1:2.5) 6.0 Sodium carboxymethyl cellulose .3 Sodium sulfate 24.2 Water 3.5

The foregoing description of the invention has been presented describing certain operable and preferred embodiments. It is not intended that the invention should be limited since variations and modifications thereof will be obvious to those skilled in the art, all of which are within the spirit and scope of this invention.

What is claimed is:

1. An antimicrobial detergent composition consisting essentially of a water-soluble detergent selected from the group consisting of fatty acid soaps, anionic organic nonsoap detergents which are water-soluble salts of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals, and amphoteric synthetic detergents which are derivatives of aliphatic amines which contain a long chain of about 8 to about 18 carbon atoms, and an anionic water-solubilizing group selected from carboxy, sulfo, or sulfato and mixtures thereof and an active antimicrobial dibenziodolium compound having the structural formula Y and Y represent radicals selected from the group consisting of halogen, nitro, alkyl radicals containing up to 3 carbon atoms, halogen substituted alkyl radicals containing up to 3 carbon atoms, amino and sulfamyl, and Y and Y can be dissimilar;

and n represent integers selected from the group consisting of 0, 1 and 2, and when n is 2, the Y radicals can be dissimilar and when n' is 2 the Y radicals can be dissimilar and,

wherein X represents an inorganic anion selected from sulfate,

bisulfate, sulfite, iodide, chloride, bromide, phosphate, biphosphite, pyrophosphate, nitrate, and nitrite or an organic anion selected from acetate, propionate, decanoate, benzoate, phenylacetate, benzenesulfonate, fumarate, lactate, tartrate, or citrate,

said active dibenziodolium compound being present in said detergent composition in an antimicrobially effective amount.

2. The antimicrobial detergent composition of claim 1 wherein the active antimicrobial dibenziodolium compound is present within the range of about .01% to about 10% by weight of the detergent composition.

3. The antimicrobial detergent composition of claim 1 wherein the active antimicrobial dibenziodolium compound is present within the range of about .05% to about 4% by weight of the detergent composition.

4. The antimicrobial detergent composition of claim 1 wherein the dibenziodolium compound is bis(3,7-dichlorodibenz(be) (1,4) oxiodinium) sulfate.

5. The antimicrobial detergent composition of claim 1 wherein the dibenziodolium compound is 3-chlorodibenz (be) 1,4)oxiodinium chloride.

6. The antimicrobial detergent composition of claim 1 wherein the dibenziodolium compound is 2-chlorodibenz (be) 1,4) oxiodiniurn chloride.

7. The antimicrobial detergent composition of claim 1 wherein the dibenziodolium compound is l-chlorodibenz (be) 1,4) oxiodinium chloride.

8. The antimicrobial detergent composition of claim 1 wherein the dibenziodolium compound is dibenz(be) (1,4)oxiodinium chloride.

9. The antimicrobial composition of claim 1 wherein the amphoteric detergent is selected from the group consisting of 3-(N,N-dimethyl-N-alkylammonio)-propane-1- sulfonate and 3-(N,N-dimethyl-N-alkylammonio)-2-hydroxy-propane-1-sulfonate, wherein the alkyl radical con tains from 12 to 18 carbon atoms.

10. An antimicrobial detergent composition consisting essentially of (a) a water-soluble detergent selected from the group consisting of fatty acid soaps, anionic organic non-soap detergents which are water-soluble salts of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals, and amphoteric synthetic detergents which are derivatives of aliphatic amines which contain a long chain of about 8 to about 18 carbon atoms, and an anionic water-solubilizing group selected from carboxy, sulfo, or sulfato and mixtures thereof; (b) an active antimicrobial dibenziodolium compound having the structural formula Yn 'n' wherein Y and Y represent radicals selected from the group consisting of halogen, nitro, alkyl radicals containing up to 3 carbon atoms, halogen substituted alkyl radicals containing up to 3 carbon atoms, amino and sulfamyl, and Y and Y' can be dissimilar;

n and n represent integers selected from the group consisting of 0, 1 and 2, and when n is 2, the Y radicals can be dissimilar and when n' is 2 the Y radicals can be dissimilar and,

wherein X represents an inorganic anion selected from sulfate,

bisulfate, sulfite, iodide, chloride, bromide, phosphate, biphosphite, pyrophosphate, nitrate, and nitrite or an organic anion selected from acetate, propionate, decanoate, benzoate, phenylacetate, benzenesulfonate, fumarate, lactate, tartrate, or citrate, said active dibenziodolium compound being present in said detergent composition in an antimicrobially effective amount, and

(c) a chlorine bleaching agent selected from sodium hypochlon'te, dichlorocyanuric acid and the sodium and potassium salts thereof; trichlorocyanuric acid; 1,3-dichloro-5,5-dimethyl hydantoin', N,N-dichlorobenzoylene urea; paratoluene sulfondichloroamide; trichloromelamine; N-chloroammeline; N-chlorosuccinimide; N,N- dichloroazodicarbonamidine; N-chloracetyl urea; N,N'- dichlorobiuret; chlorinated dicyandiamide; calcium hypochlorite; lithium hypochlorite; chlorinated trisodium phosphate at a level which provides from about .5% to about 50% available chloride.

11. A method of imparting antimicrobial properties to a cotton fabric which consists essentially of washing said fabric in an aqueous solution of an organic detergent selected from the group consisting of fatty acid soaps, anionic organic non-soap detergents which are watersoluble salts of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals, and amphoteric synthetic detergents which are derivatives of aliphatic amines which contain a long chain of about 8 to 18 carbon atoms, and an anionic water-solubilizing group selected from carboxy, sulfo, or sulfato having incorporated therein from 0.01% to 4% by weight, based on the detergent surfactant of an active antimicrobial dibenziodolium compound having the structural formula wherein Y and Y represent radicals selected from the group consisting of halogen, nitro, alkyl radicals containing up to 3 carbon atoms, halogen substituted alkyl radicals containing up to 3 carbon atoms, amino and sulfamyl, and Y and Y can be dissimilar;

and n' represent integers selected from the group consisting of 0, 1 and 2, and when n is 2, the Y radicals can be dissimilar and when n is 2 the Y radicals can be dissimilar and,

wherein X represents an inorganic anion selected from sulfate,

bisulfate, sulfite, iodide, chloride, bromide, phosphate, biphosphite, pyrophosphate, nitrate, and nitrite or an organic anion selected from acetate, propionate, decanoate, benzoate, phenylacetate, benzenesulfonate, fumarate, lactate, tartrate, or citrate.

12. A cosmetic detergent soap bar composition consisting essentially of a soap detergent and an antimicrobially effective amount of an active antimicrobial dibenziodolium compound having the structural formula n Y n X wherein Y and Y' represent radicals selected from the group consisting of halogen, nitro, alkyl radicals containing up to 3 carbon atoms, halogen substituted alkyl radicals containing up to 3 carbon atoms, amino and sulfamyl, and Y and Y can be dissimilar;

n and n represent integers selected from the group consisting of 0, 1 and 2, and when n is 2, the Y radicals can be dissimilar and when n is 2 the Y radicals can be dissimilar and,

wherein X represents an inorganic anion selected from sulfate,

bisulfate, sulfite, iodide, chloride, bromide, phosphate, biphosphite, pyrophosphate, nitrate, and nitrite or an organic anion selected from acetate, propionate, decanoate, benzoate, phenylacetate, benzenesulfonate, fumarate, lactate, tartrate, or citrate.

13. The soap bar composition of claim 12 wherein the active antimicrobial dibenziodolium compound is present within a percentage range of 0.01% to 4% by weight of the soap detergent.

References Cited by the Examiner UNITED STATES PATENTS 2,129,264 9/1938 Downing et al. 252l52 XR 2,487,799 11/1949 Gump 252107 2,878,293 3/1959 Kinzer 16770 XR 3,084,097 4/1963 Reller et al. 252107 XR 3,118,842 1/1964 Besser 252106 FOREIGN PATENTS 578,210 6/ 1946 Great Britain. 654,139 6/1951 Great Britain.

OTHER REFERENCES Freedlander: Chem. Abstract, vol. 41, pp. 2115 (1947).

Gershenfeld et al.: Amer. Jour. Pharm., May 1948, pp. 158-169.

Sandin et al.: J. Amer. Chem. Soc., vol. 74, pp. 274275, January 1952.

Collette et al.: J. Amer. Chem. Soc, vol. 78, pp. 3819-20 (1956).

ALBERT T. MEYERS, Primary Examiner.

JULIUS GREENWALD, Examiner. 

1. AN ANTIMICROBIAL DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A WATER-SOLUBLE DETERGENT SELECTED FROM THE GROUP CONSISTING OF FATTY ACID SOAPS, ANIONIC ORGANIC NONSOAP DETERGENTS WHICH ARE WATER-SOLUBLE SALTS OF ORGANIC SULFURIC REACTION PRODUCTS HAVING IN THEIR MOLECULAR STRUCTURE AN ALKYL RADICAL CONTAINING FROM ABOUT 8 TO ABOUT 22 CARBON ATOMS AND A RADICAL SELECTED FROM THE GROUP CONSISTING OF SULFONIC ACID AND SULFURIC ACID ESTER RADICALS, AND AMPHOTERIC SYNTHETIC DETERGENTS WHICH ARE DERIVATIVES OF ALIPHATIC AMINES WHICH CONTAIN A LONG CHAIN OF ABOUT 8 TO ABOUT 18 CARBON ATOMS, AND AN ANIONIC WATER-SOLUBILIZING GROUP SELECTED FROM CARBOXY, SULFO, OR SULFATO AND MIXTURES THEREOF AND AN ACTIVE ANTIMICROBIAL DIBENZIODOLIUM COMPOUND HAVING THE STRUCTURAL FORMULA 